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Issue 43, 2018
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Three microporous metal–organic frameworks assembled from dodecanuclear {NiII6LnIII6} subunits: synthesis, structure, gas adsorption and magnetism

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Abstract

Three isostructural heterometallic metal–organic frameworks (MOFs) {[Ln2Ni(OAc)5(HL)(L)]·solvent molecules}n (H2L = 2-hydroxyimino-N-[1-(2-pyrazinyl)ethylidene]-propanohydrazone, Ln = Dy for 1, Tb for 2 and Gd for 3) were solvothermally synthesized by varying rare-earth metal ions with different electron configurations. Their crystal structures, gas adsorption and magnetic behaviors were fully investigated. The three isomorphous MOFs exhibit three-dimensional microporous frameworks with two different orientated dodecane metallic {NiIILnIII(HL)}6 metallomacrocycles alternately connected by {LnIII(L)} connectors, in which an empty one-dimensional channel decorated by the basic hydrazone interior is generated. Due to their LnIII-independent microporous nature, the activated sample of 1 as a representative example has a significant CO2 uptake up to 42.2 cm3 g−1 and an unusually high CO2/N2 and CO2/CH4 adsorption selectivity of up to 98.8 and 16.8 at 298 K and 100 kPa. Magnetically, apparent antiferromagnetic interactions for both 1 and 2 as well as ferromagnetic coupling for 3 are respectively observed at low temperature resulting from the competition of magnetic anisotropy and intermetallic ferromagnetic superexchange. Additionally, 1 with highly anisotropic DyIII spin shows slow magnetization relaxation under zero dc field, whereas 3 possessing isotropic GdIII ions displays a significant cryogenic magnetocaloric effect with a maximum entropy change of 26.6 J kg−1 K−1 at 3.0 K and 70 kOe. These interesting results can provide valuable information on gas separation-based multifunctional 3d–4f MOF materials.

Graphical abstract: Three microporous metal–organic frameworks assembled from dodecanuclear {NiII6LnIII6} subunits: synthesis, structure, gas adsorption and magnetism

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Publication details

The article was received on 10 Jul 2018, accepted on 17 Sep 2018 and first published on 17 Sep 2018


Article type: Paper
DOI: 10.1039/C8DT02816H
Citation: Dalton Trans., 2018,47, 15344-15352
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    Three microporous metal–organic frameworks assembled from dodecanuclear {NiII6LnIII6} subunits: synthesis, structure, gas adsorption and magnetism

    D. Feng, H. Dong, Z. Liu, X. Zhao and E. Yang, Dalton Trans., 2018, 47, 15344
    DOI: 10.1039/C8DT02816H

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